Derivatives of fluoranthene and process of making same



Patented Aug. 26, 1941 DERIVATIVES OF FLUORANTHENE AND PROCESS OF MAKINGSAME Walter Kern, Sissach, and Theodor Holbro and Richard Toble'r,Riehen, Switzerland, assignors to Society of Chemical Industry in Basie,Basel,

Switzerland No Drawing; Application September 6, 1938, Se-

iial N 0. 228,687. In Switzerland September 14,

15 Claims.

This invention relates to the manufacture of derivatives of fiuorantheneby causing a halogen substitution product of fluoranthene to react Witha vattable compound containing at least three condensed six-memberedrings of carbon atoms, further at least one hydrogen atom bound to anitrogen atom, as well as at least one carbonyl group the carbon atom ofwhich is a member of a siX-membered ring; if desired, the productobtained may be treated with a halogenating agent.

For the reaction with halogen substitution product of fluoranthene whichmay contain 1, 2 or more halogen atoms, e. g. chlorine, bromine oriodine of the same or of diiierent kinds, for example mono-, diortetrabromofluoranthene, various compounds e. g. aromatic vattablecompounds containing at least three condensed sixmembered rings ofcarbon atoms, further at least one hydrogen atom bound to a nitrogenatom, as Well as at least one carbonyl group the carbon atom of which isa member of a six-membered ring may be used, and 1 mol of a polyhalogenfluoranthene may be caused to react with 2 or more mols of the same ordifferent i compounds, either simultaneously or in succession. Suchvattable compounds may be anthraquinone derivatives or may belong tomore highly condensed ring systems; for instance anthraquinones such asl-amino-anthraquinone and 1- amino-arylaminoanthraquinones. Alsoaminoacylaminoanthraquinones, wherein the acyl residue may be that of analiphatic, aromatic or heterocyclic acid, for example a carboxylic acid;

compounds of this latter kind are, for instance 1-amino-4abenzoylaminoanthraquinone, 1-.amino- 5.benzoylaminoanthraquinone, 1-amino-5-ben zoylamino-8methoxyanthraquinone, 1 amino 5:8-dibenzoylaminoanthraquinone, 1 eaminoan thraquinonoylaminoanthraquinone; also aminopyranthrones,aminoanthanthrones, aminoperylenequinones, aminodianthrones,amino-N-dihy- .dro-anthraquinoneazines, aminoanthraquinoneazines,aminobenzpyrenequinones, aminoflavanthrenes and aminodibenzanthrones andamino,- a.

anthraquinone derivatives in which the 1- and 9- positions are membersof a heterocyclic ring, for instance amino-1:S-anthrapyrimidines, amino-1:9 anthrapyridones, amino-1:9 isothiazolan thrones andamino-1:Q-pyrazolanthrones; finally also aminoanthraquinones in which 2carbon atoms in ortho-position to each other are members of aheterocyclic ring system as is the case, for instance, inamino-1:Z-anthraquinone-acridones. Any of these compounds may containfurther substituents.

In addition to the above mentioned aminoacylamino-anthraquinones theremay also be used acylamino compounds in which the radical diiferentorganic liquids, for example benzene,

toluene or xylol. It is of advantage to work underexclusio-n of Waterand by'using a solvent having a relatively high boiling point, forinstance amyl alcohol, nitrobenzene or -naphthalene and advantageouslyin presence of a catalyst as well as an acid binding agent. Temperaturesabove 150 C. are advantageously used. As in the following examples therehave been named mainly cuprous chloride as catalyst and sodium acetateand sodium carbonate as acid-binding agent, it is to be stated thatthese agents yield very good results,it is true, but that the processcan also be carried out with other catalysts, for

example finely divided copper or other copper compounds or other metals,or also Without catalysts, or by using otheracid-binding agents such asfor example calcium or barium carbonate or hydroxide, or also withoutacid-binding agents. All or only a part of the halogen atoms present inthe fluoranthene compound may take part in the reaction.

The fluoranthene derivatives thus obtainable correspond to the generalformula 13- (NH-R1) 1L wherein R stands for a fluoranthene radical, R1stands for a radical of a vattable compound containing at least threecondensed six-membered rings of carbon atoms, as well as at least onecarbonyl group the carbon atom of which is a member of a six-memberedring and n stands at least for the number 1.

The treatment of the product obtained with a halogenating agent, forinstance bromine, may occur with advantage in the presence of anindifferent solvent or diluent, for instance nitrobenzene.

The fluoranthene derivatives obtainable by the invention are useful asbody colors for various purposes. For the most part they are alsovaluable intermediate products for making vat dyestuffs, e. g. accordingto the process described in our copending application Serial No.228,688, while in certain instances they are themselves vat dyestuffs.

The following examples illustrate the invention; the relationshipbetween the parts by volume and the parts by weight is that between thelitre and the .kilo:

Example 1 16.8narts of 4-bromofluoranthene obtainable by rominatingfiuoranthene in carbon tetrachloride as described in Annalen der Chemie,vol. 488, page 111, 9 parts of anhydrous sodium carbonate, 9 parts ofanhydrous sodium acetate, 21 .parts of 1- aminobenzoylaminoanthraquinoneand 0.8 part of cuprous chloride are together suspended in 200 parts ofnitrobenzene which has been dried NH O H By analogous reaction of4-bromofluoranthene with l-amino 4 benzoylaminoanthraquinone there isobtained -benzoylamino-l'anthraquinoyl-4-aminoiiuoranthene of theprobable formula NH O H which is a dark green crystalline powder solublein concentrated sulfuric acid to a green solution, melting at 310-315"C. and vatted with great difficulty.

I Example 2 7.2 parts of dibroinofiuoranthene, obtainable bybromin-ating fiuoranthene in carbon bisulfide as which colorsconcentrated sulfuric acid yellow olive, has a melting point above 400C. and is vatted with great difficulty.

Example 3 7.2 parts of dibromofluoranthene, obtainable by brominatingfluoranthene, 13 parts of l-amino-4-benzoylaminoanthraquinone, 1.6 partsof cuprous chloride and 7 parts of anhydrous sodium acetate are togethersuspended in 156 parts of nitrobenzene and the whole is stirred for 16hours at a temperature of l200 0. Hot filtration and washing withnitrobenzene, benzene and alcohol follow and for removing coppercompounds the mass is extracted hot first with dilute hydrochloric acidand then with alcohol. The

condensation product which probably contains chiefly the product of theformula 18 parts of anhydrous sodium acetate and 18 parts of anhydroussodium carbonate are added to 380 parts of nitrobenzene and the whole iskept boiling until 50 parts of nitrobenzene have I distilled. Aftercooling to 200 C., 21.6 parts of dibromofluoranthene, obtainable bybrominating fluoranthene in nitrobenzene, 46 parts ofl-amino-4-benzoylaminoanthraquinone and 1.6 parts of cuprous chlorideare added and the whole is stirred for 48 hours at l95-205 0. Hotfiltration and washing with nitrobenzene, benzene and alcohol follow andthe product is further purified by extracting it with boilinghydrochloric acid, filtering, washing and drying. There is obtained avery good yield (over 95 per cent) of a greenish-black crystallinepowder which colors concentrated sulfuric acid olive, melts at 410 C.and is vatted with great difiiculty. Analysis shows that it isdi-(4-benzoyl-amino-1'-anthraquinonyl)-diaminofluoranthene of theprobable formula given in Example 3.

Example 5 'zene and with alcohol and for the further purificationextracted hot with dilute hydrochloric acid and then with alcohol,filtered, washed and dried. There is obtained a good yield of a darkbrown crystalline powder which colors concentrated sulfuric acid oliveand melts at 420 C.

,Analysis shows it to be di-(5-benzoylamino-1'- anthraquinonyl)-diaminofluoranthene probable formula Example 6 1.8 parts ofdibromofiuoranthene, 2.8 parts of 1-amino-5-acetylaminoanthraquinone,1.5 parts of anhydrous sodium acetate, 1.5 parts of anhydrous sodiumcarbonate and 0.15 part of cuprous chloride are together suspended in 60parts of dry nitrobenzene and the whole is heated to boiling whilestirring. When the reaction is complete, the mass is filtered hot andthe solid matter is washed with nitrobenzene, benzene and alcohol,extracted hot with dilute hydrochloric acid, filtered, washed and dried.There is obtained a good yield of a black-red crystalline powder of theprobable formula 1 NH O O NH-COCHs soluble in concentrated sulfuric acidto an olive green solution which does not melt below 450 C. and can bevatted only with great difiiculty.

In similar manner there is obtained from 1 mol dibromofiuoranthene and 2mols l-amino- 5- (para-chloro) -benzcylaminoanthraquinone a brown powdersoluble in" concentrated sulfuric acid to an olive brown solutionmelting at 390-400 C. and not capable of being vatted.

The product of the reaction of 1 mol dibromofluoranthene with 2 mols1-amino-5-cinnamoylaminoanthraquinone is a brown crystalline pow dersoluble in concentrated sulfuric acid to an olive green solution,melting with decomposition at 360-365 C. and capable of being vattedwith great difficulty.

From dibromofiuoranthene and l-amino-E-fi-'anthraquinonoylamincanthraquinone there is of the obtained in analogousmanner ablack powder of the probable formula which does not melt at 450C., is soluble in concentrated sulfuric acid to an olive brown solutionand dyes cotton in a brown vat blackish olive tints.

Excample 7 12 parts of anhydrous sodium acetate, 12 parts of anhydroussodium carbonate, 10.4: parts of tetrabromofiuoran-thene, 27.4 parts ofl-amino- 4-benzoylaminoanthraquinone and 1.1 parts of cuprous chlorideare together suspended in 225 parts of dry nitrobenzene and the mixtureis stirred for 22 hours at 190200 C. The whole is filtered hot and thesolid matter is washed with nitrobenzene, benzene and alcohol, and forfurther purification extracted hot with dilute hydrochloric acid andwith alcohol; it is then filtered, Washed and dried. There is obtained aL black powder which colors concentrated sulfuric acid green and doesnot melt at 460 C. yet analysis shows it to be atetra-(4'-benzolamino-1'- anthraquinonyl)-tetraminofiuoranthene of theprobable formula The tetrabromofluoranthene used in this example is madeas follows: 101 parts of fluoran- 'thene are dissolved in 830 parts ofnitrobenzene and there are added while stirring and in the course of 4hour 324 parts of bromine. The mixture is heated in the course of 2hours to 125 C.

and stirred at this temperature for 3 hours. After cooling to 60 C., thewhole is filtered and the solid matter is pressed, Washed with alcoholand recrystallised from Xylene. Tetrabromofiuoranthene is thus obtainedin the form of small yellow needles which melt at 304-306" C.

Example 8 6 parts of anhydrous sodium acetate, 6 parts of anhydroussodium carbonate, 10.4 parts of tetrabromofiuoranthene, obtained asdescribed in Example 7, paragraph 2, 13.? parts or"l-aminolbenzcylaminoanthraquinone and 0.6 part of cuprous chloride aretogether suspended in 165 parts of dry nitrobenzene and the whole, is

stirred for 22 hours at 190-200 C. It is then filtered hot and the solidmatter washed with nitrobenzene, benzene and alcohol, further purifiedby hot extraction with dilute hydrochloric acid and then with alcohol;it is finally filtered, Washed and dried. It is a black powder whichcolors concentrated sulfuric acid olive and does not melt at 460 C. yetanalysis shows it to be a dibromo di -(4'- benzoylamino 1-anthraquinonyD-diaminofiuoranthene of the probable formula Example 9 2.7parts of dibromofluoranthene, obtainable by brominating fluoranthene innitrobenzene, 5.1 parts of 4-ar'ninoanthraquinone-2: 1 (N)-benzeneacridone, 2.3 parts of anhydrous sodium acetate, 2.3 parts ofanhydrous sodium carbonate and 0.2 part of cuprous chloride are togethersuspended in 60 parts of nitrobenzene and the Whole is heated to boilingwhile stirring. When the reaction is complete, the mass is filtered hotand the solid matter is washed with nitrobenzene, benzene and alcoholand extracted with boiling dilute hydrochloric acid; it is then filteredand dried. The dyestufl of the probable formula which is obtained ingood yield is a dark bluegreen crystalline powder which melts at 425-430C. It dissolves in concentrated sulfuric acid to a brown solution anddyes'cotton in a violet-red vat yellow-olive tints.

Example 10 10.8 parts of dibromofiuoranthene, 19 parts of1amino-l--ani1inoanthraquinone, 0.8 part of cuprous chloride, 9 parts ofanhydrous sodium acetate and 9 parts of anhydrous sodium carbonate aretogether mixed with 250 parts of dry nitrobenzene and the whole isheated to boiling while stirring; when the reaction is complete, theproduct is worked up in the usual manner.

9,253,739 it is a black crystalline powder of the probable formula NENEG which melts at 410 C. with decomposition, is not capable of beingvatted and dissolves in concentrated sulfuric acid to a blue solution.

By corresponding reaction of 1 mol dibromofluoranthene with 2 mols1-amino-4-methoxyanthraquinone, there is obtained a black crystallinepowder which decomposes at about 400 C., dissolves in concentratedsulfuric acid to a blue solution and is not capable of being vatted.

Example 11 5.4 parts of dibromofiuoranthene are caused to react with 15parts of aminodibenzanthrone in presence of 0.2 part of cuprouschloride, parts of anhydrous sodium carbonate and 5 parts of anhydroussodium acetate in 360 parts of boiling nitrobenzene. The product workedup in the usual manner is a dark green crystalline powder of theprobable formula F a j il] which does not melt below 450 C., dissolvesin concentrated sulfuric acid to a blackish-red solution and dyes cottongrey-black in a blue vat.

Example 12 3.6 parts of dibromofluoranthene, 5.6 parts of4-amino-N-methyl-1,9-anthrapyridone, 3 parts of anhydrous sodiumcarbonate, 3 parts of anhydrous sodium acetate and 0.3 part of ouprouschloride are together heated for 40 hours in 84 parts of boilingnitrobenzene while stirring. The mass is filtered hot and the solidmatter purified in the usualmanner. There is obtained in good yield abluish black crystallme powder of the probable formula Gila-I l CHsoluble in concentrated sulfuric acid to a blue solution, meltingabove-450 .C. and incapable of being vatted.

In corresponding manner there is obtained from 1 :moldibromofluoranthene and 2 mols 5 -aminoisothiazoleanthrone, a darkviolet-brown crystalline powder of the probable formula which *meltswith decomposition at 420-425 C., is vatted only with great difii'cultyanddissolves in concentrated sulfuric acid to an olive solution. With4-aminopyrazo1anthrone there is obtained a brown powder of the probableformula of being vatted, and dissolves to a yellow-red solution inconcentrated sulfuric acid.

Example 13 3.6 parts of'dibromofiuoranthene, 5 parts of 5-amino-1,9-anthrapyrimidine, 3 parts of anhydrous sodium carbonate, 3parts of anhydrous sodium acetate and 0.3 part of cuprous chloride aretogether heated for 40 hours while stirring in84parts of boilingnitrobenzene. The mass'is filtered hot and the solid matter purified asusual.

There is obtained in very good yield a black-blue crystalline powder ofthe probable formula Example 14 11.9 parts of dibrornofluoranthene, 19.3parts of 1-amino-4-benzoy1aminoanthraquinone, 0.4 part of cuprouschloride, 4.5 parts of anhydrous sodium carbonate and 4.5 parts ofanhydrous sodium acetate are together suspended in 275 parts of drynitrobenzene and the whole is heated gradually in the course of 32 hoursfrom 120 C. to 180 C. The mass is then filtered hot. From the filtratethere separates on cooling a green-black crystalline powder which, afterfiltration, washing and drying, melts with decomposition at 270280 C.dissolves in concentrated sulfuric acid to a brown solution and is notcapable of being vatted. Analysis shows that it is then1ono-(4benzoylamino-l-anthraquinony1) -amino-mono brornofiuoranthene ofthe probable formula Br The mono- (5 -benzoylamino-1 -anthraquinonyl)amino-mono-bromofluoranthene is obtained in analogous manner. It is ablack-brown crystalline' powder which melts at 295300 C., dissolves inconcentrated sulfuric acid to a brown solution and is not capable ofbeing vatted.

Example 15 If the mono- (4-benzolyaminoanthraquinonyl)amino-mono-bromofiuoranthene, obtained as described in paragraph 1 ofExample 14, is caused to react in the usual manner with a second mol of1-amino-4-benzoylaminoanthraquinone, there is obtained the same productas is produced in Example 4.

If 1-amino-5-benzoylaminoanthraquinone is used, there is obtained ablack crystalline powder v of the probable formula yearwhich melts at365-370 C., dissolves in concen trated sulfuric acid to a brown-olivesolution Example 16 3.1 parts of the product of the reaction of 1 moldibromofluoranthene with 1 mol of l-amino- 4-benzoylamino-anthraquinone(obtainable as described in Example 1 1, paragraph 1), 1.3 parts of 5amino -isothiazolan throne, 0.1 part of cuprous chloride, 0.8 partofanhydrous sodium acetateand 0.3 part of anhydrous sodium carbonate aresuspended together in 60 parts of dry hitrobenzene and the whole isstirred at the boiling temperature for 24 hours. The mass is thenfiltered hot and the solid matter washed With nitrobenzene, benzene andalcohol, extracted with boiling hydrochloric acid and dried. Theviolet-black powder thus obtained melts at 420-425" C., dissolves inconcentrated sulfuric acid to a brown-olive solution and is not capableof being vatted.

If 4-amino-N-methyl 1,9 anthrapyridone is used instead of5-amino-isothi-azolanthrone there is obtained a black crystalline powderwhich melts at 380-385 C. with decompositon; it dissolves inconcentrated sulfuric acid to a blackred solution and is not capable ofbeing vatted.

With 5-amino-1,9-anthrapyrimidine there is obtained a black crystallinepowder which melts at 405-415 (3., produces in strong sulfuric acid anolive color and is vatted only with difiiculty. The product of reactionwith 4-amino-L9- anthrapyrimidine is also a black crystalline powderwhich melts at 380 C., dissolves in concentrated sulfuric acid to abrown solution and is vatted only with great difficulty.

What we claim is:

1. Process for the manufacture of derivatives of fiuoranthene,comprising causing halogen substitution products of fluoranthene toreact with vattable compounds containing at least three condensedsix-membered rings of carbon atoms, further at least one carbonyl groupthe carbon atom of which is a member of a six-membered ring as well asat least one amino group selected from the class consisting of primaryand secondary amino groups directly attached to a carbon atom of thecondensed ring system.

2. Process for the manufacture of derivatives of fiuoranthene,comprising causing dihalogen substitution products of fiuoranthene toreact with vattable compounds containing at least three condensedsix-membered rings of carbon atoms, further at least one carbonyl groupthe carbon atom of which is a memberof a six-membered ring as well as atleast one amino group,

selected from the class consisting of primary and secondary amino groupsdirectly attached to a carbon atom of the condensed ring system.

3. Process for the manufacture of derivatives of fluoranthene,comprising causing dibromo substitution products of fluoranthene toreact with vattable compounds containing at least three condensedsix-membered rings of carbon atoms, further at least one carbonyl groupthe carbon atom of which is a member of a siX-membered ring as well asat least one amino group selected from the class consisting of primaryand secondary amino groups directly attached to a carbon atom of thecondensed ring system.

l. Process for the manufacture of derivatives of fluoranthene,comprising causing 1 mol of a dibromo substitution product offluoranthene to react with 2 mols of vattable compounds containing atleast three condensed six-membered rings of carbon atoms, further atleast one carbonyl group the carbon atom of which is a member of asix-membered ring as Well as a primary amino group directly attached toa carbon atom of the condensed ring system.

5. Process for the manufacture of derivatives of fiuoranthene,comprising causing 1 mol of a dibromo substitution product offluoranthene to react with 2 mols of an aminoacylaminoanthraquinone.

6. Process for the manufacture of derivatives of fiuoranthene,comprising causing 1 mol of a dibromo substitution product offluoranthen'e to react with 2 mols of1-amino-5-benzoylaminoanthraquinone.

7. Process for the manufacture of derivatives of fluoranthene,comprising causing 1 mol of a dibromo substitution product offluoranthene to react with 2 mols of l-aminoi-benzoylaminoanthraquinone.

8. Process for the manufacture of derivatives of fiuoranthene,comprising causing 1 mol of a dibromo substitution product offiuoranthene to react with 2 mols of 4-aminoanthraquinone 2:1- (N)-benzacridone.

9. Fluoranthene derivatives of the general formula wherein R stands fora fiuoranthene radical, R1 stands for a radical of a vattable compoundcontaining at least three condensed six-membered rings of carbon atomsas well as at least one carbonyl group the carbon atom of which is amember of a six-membered ring and it stands for one of the numbers 1 to4 inclusive.

l0. Fluoranthene derivatives of the general formula R1NH-RNH-Rz whereinR stands for a fiuoranthene radical, R1 and R2 stand for radicals ofvattable compounds containing at least three condensed six-memberedrings of carbon atoms, as Well as at least one carbonyl group the carbonatom of which is a member of a six-membered ring.

11. Fluoranthene derivatives of the general formula wherein R stands fora fiuoranthene radical and R1 and R2 stand for anthraquinone radicals.

12. Fluoranthene derivatives of the general formula wherein R stands fora fluoranthene radical and R1 and R2 stand for acylaminoanthraquinoneradicals.

13. Fluoranthene derivatives of the formula 14. Fluoranthene derivativesof the formula 15. Fluoranthene derivatives of the formula WALTER KERN.THEODOR HOLBRO. RICHARD TOBLER.

